EP0736540A2 - Oxydes de mono- et diacylphosphines - Google Patents

Oxydes de mono- et diacylphosphines Download PDF

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Publication number
EP0736540A2
EP0736540A2 EP96107166A EP96107166A EP0736540A2 EP 0736540 A2 EP0736540 A2 EP 0736540A2 EP 96107166 A EP96107166 A EP 96107166A EP 96107166 A EP96107166 A EP 96107166A EP 0736540 A2 EP0736540 A2 EP 0736540A2
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EP
European Patent Office
Prior art keywords
alkyl
alkoxy
phenyl
halogen
mono
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96107166A
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German (de)
English (en)
Other versions
EP0736540A3 (fr
Inventor
Werner Dr. Rutsch
Kurt Dr. Dietliker
Roger Graham Dr. Hall
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba Geigy AG
Ciba Spezialitaetenchemie Holding AG
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Publication of EP0736540A2 publication Critical patent/EP0736540A2/fr
Publication of EP0736540A3 publication Critical patent/EP0736540A3/fr
Withdrawn legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/32—Esters thereof
    • C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/3247—Esters of acids containing the structure -C(=X)-P(=X)(R)(XH) or NC-P(=X)(R)(XH), (X = O, S, Se)
    • C07F9/3252—Esters of acids containing the structure -C(=X)-P(=X)(R)(XH) or NC-P(=X)(R)(XH), (X = O, S, Se) containing the structure -C(=X)-P(=X)(R)(XR), (X = O, S, Se)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5337—Phosphine oxides or thioxides containing the structure -C(=X)-P(=X) or NC-P(=X) (X = O, S, Se)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
    • C07F9/65685—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine oxide or thioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents

Definitions

  • the invention relates to special mono- and diacylphosphine oxides and their use as photoinitiators for the photopolymerization of ethylenically unsaturated compounds.
  • R 1 , R 2 , R 3 and R 4 as C 1 -C 18 alkyl can be branched or unbranched alkyl and can be, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, Hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl or octadecyl.
  • R 3 as alkyl is preferably tertiary alkyl, such as, for example, tert-butyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl or 1,1,3,3-tetramethylbutyl.
  • R 1 and R 2 as C 2 -C 18 alkenyl can be, for example, vinyl, allyl, methallyl, 1,1-dimethylallyl, 2-butenyl, 2-hexenyl, octenyl, undecenyl, dodecenyl or octadecenyl.
  • R 4 as C 2 -C 18 alkenyl can also be vinyl.
  • R 3 as C 2 -C 6 alkenyl can be, for example, vinyl, propenyl or butenyl.
  • Substituted C 1 -C 8 alkyl can, for example, benzyl, 1-phenylethyl, 2-phenylethyl, ⁇ , ⁇ -dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butylphenyl) -ethyl, p-chlorobenzyl, 2,4- Dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di (methoxycarbonyl) ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2 -Butoxyethyl, diethoxymethyl, diethoxyethyl, 1,3
  • R 3 as mono- or polysubstituted, for example mono- to trisubstituted, in particular mono- or polysubstituted, substituted C 1 -C 8 -alkyl can be, for example, benzyl, phenylethyl, ⁇ , ⁇ -dimethylbenzyl, benzhydryl, 1,1-dichloroethyl, Trichloromethyl, trifluoromethyl, 1,1-dimethyl-2-chloroethyl, 2-methoxyisopropyl, 2-ethoxyethyl, butylthiomethyl, 2-dodecylthioethyl or 2-phenylthioethyl.
  • R 4 as mono- or polysubstituted, for example mono- to trisubstituted, in particular mono- or polysubstituted, substituted C 1 -C 8 -alkyl can be, for example, benzyl, 2-phenylethyl, 3-phenylpropyl, 2-methoxyethyl, 2-butoxyethyl, 2-Hexyloxyethyl, 2-isopropoxypropyl, 2-chloroethyl or 2,2,2-trifluoroethyl.
  • R 1 , R 2 , R 3 and R 4 as C 5 -C 8 cycloalkyl can be, for example, cyclopentyl, cyclohexyl or cyclooctyl.
  • R 3 as substituted for example one to 4 times C 5 -C 10 cycloalkyl can, for example methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, Dimethoxycyclohexyl, Diethoxycyclohexyl, Butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl or dichlorocyclopentyl or a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl.
  • R 1 , R 2 , R 3 and R 4 as C 6 -C 12 aryl can be, for example, phenyl, ⁇ -naphthyl, ⁇ -naphthyl or 4-diphenylyl, in particular phenyl.
  • R 1 , R 2 and R 3 as substituted C 6 -C 12 aryl can be, for example, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, tolyl, ethylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, isopropylnaphthyl, isopropylnaphthyl, isopropylnaphthyl, isopropylnaphthyl, isopropylnaphthyl, isopropylnaphthyl, isopropylnaphthyl, isopropylnaphthyl, isopropy
  • R 3 as substituted aryl can also be, for example, methoxyethylphenyl, ethoxymethylphenyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.
  • Substituted aryl is also preferably substituted phenyl.
  • R 1 , R 2 and R 3 as a heterocyclic radical can be, for example, furyl, thienyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl or benzthiazolyl.
  • a heterocyclic radical preferably contains 3-12, in particular 3-5, carbon atoms.
  • Substituted (for example with 1-3, in particular 1 or 2, substituents) heterocyclic radicals are, for example, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl or difluoropyridyl.
  • X as C 1 -C 6 alkylene can be, for example, methylene, 1,2-ethylene, 2,2-dimethyl-1,3-propylene, tri-, tetra-, penta- and hexamethylene or phenylmethylene.
  • R 1 and R 2 together with the P atom form a monocyclic ring, this is preferably a phosphacyclopentane ring. If R 1 and R 2 together with the P atom form a bicyclic ring, this is preferably a phosphabicyclohexane or bicyclononane ring.
  • R 1 and R 4 together with the P atom form a tricyclic ring this is preferably a (6H) -dibenz [c, e] [1,2] -oxaphosphorin ring.
  • R 1 is preferably a substituted alkyl radical as defined above, in particular by phenyl, (C 1 -C 4 -alkyl) -phenyl, or C 1 -C 4 -alkoxy mono- or disubstituted C 1 -C 4 -alkyl, particularly preferred is benzyl.
  • R 3 is in particular a phenyl radical which is substituted in both ortho positions by C 1 -C 4 alkyl, C 1 -C 4 alkoxy or chlorine.
  • Bicyclic compounds of the formula II or III are also preferred in which n is 1-8 and R 3 has one of the meanings given above, in particular those compounds of the formula II or III, in which n is 1-8, in particular 1-4, and R 3 is C 1 -C 4 -alkyl substituted by phenyl , C 6 -C 10 aryl or phenyl which is mono- to trisubstituted by C 1 -C 12 alkyl, C 1 -C 4 alkoxy, or chlorine.
  • the reaction can be carried out with or without a solvent. If components IV and V are liquid, the process is preferably carried out without a solvent. Suitable solvents are especially hydrocarbons such as alkanes and alkane mixtures, benzene, toluene or xylene. The reaction is preferably carried out at 20-120 ° C. The resulting R 4 Cl is preferably distilled off continuously during the reaction. If a solvent is used, it is distilled off at the end of the reaction. The crude reaction product can be purified, for example, by distillation, crystallization or chromatography.
  • the phosphonites IV can be prepared in a known manner by reacting a dichlorophosphine R 1 -PCl 2 with at least 2 moles of R 4 OH in the presence of an HCl acceptor (see Houben-Weyl, Methods of the Org. Chemie XII / 1 324-327 (1963), G. Thieme-Verlag, Stuttgart).
  • the compounds of the formula I in which R 2 is a -COR 3 radical can be prepared by double acylation of a primary phosphine VI with at least 2 equivalents of an acid chloride V in the presence of at least 2 equivalents of a base and subsequent oxidation of the resulting diacylphosphine VII to the phosphine oxide according to the scheme:
  • Suitable bases are e.g. tertiary amines, alkali metals, lithium diisopropylamide, alkali alcoholates or alkali hydrides.
  • the first reaction stage is preferably carried out in solution.
  • Hydrocarbons are particularly suitable as solvents, e.g. Alkanes, benzene, toluene or xylene.
  • the phosphine VII can be isolated by evaporation or the second reaction stage is carried out without isolating VII with the solution of the crude product.
  • Particularly suitable oxidizing agents for the second stage are hydrogen peroxide and organic peroxy compounds, for example peracetic acid.
  • the primary phosphines VI used as starting material are known compounds or can be prepared in analogy to known compounds (see Houben-Weyl, Methods of Org. Chemie XII / 1, 60-63 (1963), G. Thieme-Verlag, Stuttgart) .
  • the starting phosphines VIII can be obtained by known methods, for example by reduction of monochlorophosphines (R 1 ) (R 2 ) PCl using LiAlH 4 (see Houben-Weyl, Methods of Org. Chemie XII / 1, 60-63 (1963), G. Thieme-Verlag, Stuttgart).
  • R 5 represents an alkyl radical
  • the starting materials IX can be prepared by known methods, for example by alcoholysis of monochlorophosphines (R 1 ) (R 2 ) PCl with R 5 OH in the presence of bases (see Houben-Weyl, Methods of Org. Chemie XII / 1, 208- 210 (1963), G. Thieme-Verlag, Stuttgart).
  • the compounds of formula I can be used as photoinitiators for the photopolymerization of ethylenically unsaturated compounds or mixtures which contain such compounds.
  • the unsaturated compounds can contain one or more olefinic double bonds. They can be low molecular weight (monomeric) or higher molecular weight (oligomeric).
  • Examples of monomers with a double bond are alkyl or hydroxyalkyl acrylates or methacrylates, e.g. Methyl, ethyl, butyl, 2-ethylhexyl or 2-hydroxyethyl acrylate, isobornyl acrylate, methyl or ethyl methacrylate.
  • acrylonitrile acrylamide, methacrylamide, N-substituted (meth) acrylamides
  • vinyl esters such as vinyl acetate
  • vinyl ethers such as isobutyl vinyl ether, styrene, alkyl and halostyrenes
  • N-vinyl pyrrolidone vinyl chloride or vinylidene chloride.
  • Examples of monomers with several double bonds are ethylene glycol, propylene glycol, neopentyl glycol, hexamethylene glycol or bisphenol A diacrylate, 4,4'-bis (2-acryloyloxyethoxy) diphenylpropane, Trimethylolpropane triacrylate, pentaerythritol triacrylate or tetraacrylate, vinyl acrylate, divinylbenzene, divinylsuccinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate or tris (2-acryloylethyl) isocyanurate.
  • oligomeric polyunsaturated compounds examples include acrylated epoxy resins, acrylated polyethers, acrylated polyurethanes or acrylated polyesters.
  • unsaturated oligomers are unsaturated polyester resins, which are usually produced from maleic acid, phthalic acid and one or more diols and have molecular weights of approximately 500 to 3000. Such unsaturated oligomers can also be referred to as prepolymers.
  • the prepolymer is primarily decisive for the properties of the lacquer film; through its variation, the person skilled in the art can influence the properties of the hardened film.
  • the polyunsaturated monomer acts as a crosslinker, which makes the paint film insoluble.
  • the monounsaturated monomer acts as a reactive diluent that lowers viscosity without the use of a solvent.
  • Such two- and three-component systems based on a prepolymer are used both for printing inks and for lacquers, photoresists or other photocurable compositions.
  • One-component systems based on photo-curable prepolymers are also often used as binders for printing inks.
  • Unsaturated polyester resins are mostly used in two-component systems together with a monounsaturated monomer, preferably with styrene.
  • Specific one-component systems are often used for photoresists, e.g. Polymaleimides, polychalkones or polyimides, as described in DE-OS 2 308 830.
  • the unsaturated compounds can also be used in a mixture with non-photopolymerizable film-forming components. These can be, for example, physically drying polymers or their solutions in organic solvents such as nitrocellulose or cellulose acetobutyrate. However, these can also be chemically or thermally curable resins, such as polyisocyanates, polyepoxides or melamine resins. The use of thermally curable resins is for use in so-called Hybrid systems of importance, which are photopolymerized in a first stage and crosslinked in a second stage by thermal aftertreatment.
  • the photopolymerizable mixtures can contain various additives.
  • thermal inhibitors which are intended to prevent premature polymerization, e.g. Hydroquinone or hindered phenols.
  • To increase dark storage stability e.g. Copper compounds, phosphorus compounds, quaternary ammonium compounds or hydroxylamine derivatives can be used.
  • paraffin or similar wax-like substances can be added, which migrate to the surface at the start of the polymerization.
  • Small amounts of UV absorbers such as e.g. those of the benzotriazole, benzophenone or oxalanilide type can be added. It is even better to add light stabilizers that do not absorb UV light, e.g. of sterically hindered amines (HALS).
  • HALS sterically hindered amines
  • mixtures of two or more of the photoinitiators according to the invention may be advantageous to use mixtures of two or more of the photoinitiators according to the invention.
  • mixtures with known photoinitiators can also be used, e.g. Mixtures with benzophenone, acetophenone derivatives, benzoin ethers or benzil ketals.
  • Amines can be added to accelerate the photopolymerization, e.g. Triethanolamine, N-methyl-diethanolamine, ethyl p-dimethylaminobenzoate or Michler's ketone.
  • the effect of the amines can be enhanced by adding aromatic ketones of the benzophenone type.
  • the photopolymerization can also be accelerated by adding photosensitizers which shift or broaden the spectral sensitivity.
  • photosensitizers which shift or broaden the spectral sensitivity.
  • aromatic carbonyl compounds such as Benzophenone, thioxanthone, anthraquinone and 3-acylcoumarin derivatives as well as 3- (aroylmethylene) thiazolines.
  • additives are fillers, pigments, dyes, wetting agents or leveling agents.
  • the photopolymerizable compositions advantageously contain the photoinitiator (b) in an amount of 0.05 to 15% by weight, preferably 0.2 to 5% by weight, based on the composition.
  • the photopolymerizable compositions can be used for various purposes, for example as printing ink, as white lacquer, as paint, as paint for exterior painting, for photographic reproduction processes, for image recording processes or for the production of printing plates, as dental fillings, as adhesives, as coatings for optical fibers, for printed circuits or for coating electronic parts.
  • the polymerization takes place according to the known methods of photopolymerization by irradiation with sunlight or with light which is rich in short-wave radiation.
  • light sources e.g. Medium-pressure mercury, high-pressure and low-pressure lamps, superactinic fluorescent tubes, metal halide lamps or lasers are suitable, the emission maxima of which are in the range between 250 and 450 nm.
  • longer-wave light or laser beams up to 600 nm can also be used.
  • Example 6 Initiator reactivity in a white lacquer thick film
  • Two percent by weight of the photoinitiator to be tested are incorporated into the white lacquer and the formulation is applied in a layer thickness of 100 ⁇ m to aluminum sheets which are primed with a white coil-coat lacquer.
  • the samples are cured under a medium pressure mercury lamp (Hanovia, 80 W / cm). The hardening takes place when the underside of a separated lacquer film is dry.
  • To measure the reactivity the number of passes under the lamp is determined at a certain belt speed. The reactivity is also measured after a pre-exposure of one minute under 5 40 W lamps (Philips TL03).
  • the pendulum hardness (according to König, DIN 53157), the yellowing (Yellowness Index, ASTM D1925-70) and the gloss at 20 ° and 60 ° (multigloss device, ASTM D 523) are determined immediately after curing and after an additional irradiation of 15 Minutes or 16 h (gloss) measured under 5 lamps of 40 W (Philips TL03). The results are shown in Tables 1 and 2.
  • Table 1 White lacquer thick film without pre-exposure Connection according to the example Smudge resistance * Pendulum hardness [sec] Yellowness index Gloss (20/60 °) right away after 15 min. right away after 15 min. right away after 16 h 2nd 6 43 70 1.2 0.8 78/90 77/90 1 7 36 90 1.1 0.8 81/91 79/92 * as number of passes at 20 m / min.
  • Table 2 White lacquer thick film with pre-exposure Connection according to the example Smudge resistance * Pendulum hardness [sec] Yellowness index Gloss (20/60 °) right away after 15 min. right away after 15 min. right away after 16 h 1 7 35 76 1.6 1.2 81/91 80/91 2nd 8th 38 56 1.8 1.4 59/89 58/89 * as number of passes at 20 m / min.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Polymerisation Methods In General (AREA)
  • Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
EP96107166A 1989-08-04 1990-07-27 Oxydes de mono- et diacylphosphines Withdrawn EP0736540A3 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH2897/89 1989-08-04
CH289789 1989-08-04
EP90810574A EP0413657B1 (fr) 1989-08-04 1990-07-27 Oxydes de mono- et diacyl phosphines

Related Parent Applications (2)

Application Number Title Priority Date Filing Date
EP90810574A Division-Into EP0413657B1 (fr) 1989-08-04 1990-07-27 Oxydes de mono- et diacyl phosphines
EP90810574.5 Division 1990-07-27

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EP0736540A2 true EP0736540A2 (fr) 1996-10-09
EP0736540A3 EP0736540A3 (fr) 1997-06-18

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EP96107166A Withdrawn EP0736540A3 (fr) 1989-08-04 1990-07-27 Oxydes de mono- et diacylphosphines

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EP (2) EP0413657B1 (fr)
JP (1) JP2973130B2 (fr)
KR (1) KR0168328B1 (fr)
CA (1) CA2022587C (fr)
DD (1) DD298405A5 (fr)
DE (1) DE59010615D1 (fr)
ES (1) ES2098260T3 (fr)
RU (2) RU2071610C1 (fr)

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RU2057759C1 (ru) 1996-04-10
KR0168328B1 (ko) 1999-03-20
DE59010615D1 (de) 1997-02-06
EP0413657A3 (en) 1992-03-18
EP0736540A3 (fr) 1997-06-18
ES2098260T3 (es) 1997-05-01
JP2973130B2 (ja) 1999-11-08
DD298405A5 (de) 1992-02-20
EP0413657A2 (fr) 1991-02-20
JPH03101686A (ja) 1991-04-26
KR910004641A (ko) 1991-03-29
CA2022587A1 (fr) 1991-02-05
EP0413657B1 (fr) 1996-12-27
RU2071610C1 (ru) 1997-01-10

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